Amide-glycamine condensation products



Patented Sept. 29, 1953 UNE'EES STATES I AMIDE-GLYCAMTNE CONDENSATIUN PRODUCTS No Drawing. Application October 20, 1949, Serial No. 122,570

My invention relates to a new group of chemical compounds. More particularly, it relates to addition products of fatty amides and glycamines which possess extraordinary detergent and emulsifying properties.

I have discovered that a new class of surface active agents, some possessing extraordinary detergent powers and others outstanding emulsifying properties, can be produced by a chemical addition reaction between the hydroxylalkylamide of a fatty acid and glycamine or a N-monoalkylated glycamine. These new compounds are prepared by heating together equimolecular proportions of a fatty amide and the glycamine to a temperature in the range of 120 C. to 150 C. The time required for the reaction to go to substantial completion will vary with the temperature employed and the exact chemical structure of the individual components. Within the range 120 C to 150 0., however, the time required for the completion of the reaction will seldom exceed about 4 hours.

The fatty amides which are used in producing my new compounds are those having the structural formula:

wherein R represents the hydrophobic residue of a carboxylic acid having 8 to 30 carbon atoms, R and R represent hydrogen or radicals selected from the group consisting of unsubstituted alkyl radicals containing 1-6 carbon atoms, and alkyl radicals containing a similar number of carbon atoms and substituted by one or-more hydroxyl groups as substituents, at least one hydroxyl group being present in either R or R Specific examples of radicals of the type covered in the definition of R include the straight chain saturated alkyl radicals from 071115 to 0171-135 and the straight chain olefinic radical C17H33 as well as radicals of other carboxylic acids having surface active properties such as, for example, rosin acids, :alkylbenzoic acids, alkylphenoxyacetic acids, napthenic acid, hydroxylated long chain fatty acids such as ricinoleic acid, etc. A specific example of a fatty amide of the above type is the bis-Z-hydroxyethylamide of cocoanut fatty acid, represented by the formula:

where R consists mainl of C-iiHg; and (3 1-1127 Claims. (Cl. 260-211) radicals but also-contains radicals of the C8, C10,

C16 and C18 saturated fatty acids in minor proportions. Examples of the suitable materials include the tris hydroxymethyDmethylamide of lauric acid, the Z-hydroxyethylamide of lauric acid, the bis-Z-hydroxyethylamide of myristic acid, the bis-Z-hydroxyethylamide of palmitic acid, and the like.

The fatty amides from which I prepare my new :compounds are, in general, waxy substances which are swellable or dispersible in water, although many of the satisfactory fatty amides are quite indispersible in water, an example of the latter being the 2-hydroxyethylamide of palmitic acid. These fatty amides are, for the most part,

ineffective as detergents although some of the more highly hydroxylated compounds of the class which I use in the production of my new compounds may have moderate detergent and surface active properties.

As the other component in the reaction whereby my new compounds are produced I employ a glycamine represented by the generic formula wherein R represents hydrogen or an alkyl radical containing 1-6 carbon atoms and which may contain one or more hydroxyl groups but in no case should the hydroxyl group be on the alpha carbon, and G represents the radical of a glycitol, or in other words a glycityl radical having at least 5 carbon atoms. These glycamines can be produced by hydrogenating a mixture comprising a sugar and ammonia or a primar amine as described by Flint and Salzberg in U. S. Patents Nos. 2,016,962 and 2,016,963. Examples of such materials include glucamine, N -methylglucamine, N-ethylglucamine, N(2-hydroxyethyl)glucamine, xylamine, N-methylxylamine, N-butylglucamine, N-methylgalactamine, N-methylfructamine and the like, as well as other similar materials produced by hydrogenating a mixture of a sugar such as erythose, ribose, arabinose, rhammose, mannose, gluose, lactose, sorbose, etc. and an amine such-as ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, benzylamine, dodecylamine, octadecylamine.

In producing my new compositions by the reaction of the amides of fatty acids with glycamine the progress of the reaction is evidenced. by the marked increase in surface activity of samples of the reaction mixture as Well as by changes in the physical state of the reaction mixture. For example, when myristobis (2-hydroxyethyl) amide and glucamine are mixed the reaction mass in the initial stages consists of two immiscible molten liquid phases. A representative sample of the total reaction mass at this stage shows no detergent power, and possesses only the relatively feeble surface activity of myristobis-(2- hydroxyethyl) amide itself. As the reaction proceeds, however, especially if stirring is used-to promote contact between the two liquid phases, one of the liquid phases disappears and the clear homogenous product shows a very high order of detergency and surface activity.

If less than one molecular equivalent of the glycamine is used for each molecular equivalent of fatty amide the desired condensation product will form but there will be an excess of the amide remaining in the final reaction product. Unless the percentage of this excess amide is too high it can generally be allowed to remain without seriously impairing the properties of the reaction product if it is to be used for its detergent or surface active properties, I have, for example, been able to produce a highly effective detergent by heating 1 gram molecule of myristobis-(2-hydroxyethyl)amide and 0.7 gram molecule of N-methylglucamine. When using the reactants in such proportions there appears to be approximately 20% of free myristobis-(Z- hydroxyethyl) amide in the final product but the surface activity of the total composition is still high. I have found it preferable to use the specified reactants in approximately equimolecular proportions.

While our new composition may be used for various purposes they possess unusual utility as surface active agents. The specific surface active effects for which they are useful depend on the chemical structure of both starting materials. Some of iny new compounds possess properties which make them excellent detergents for woolen fabrics. Still others serve as excellent detergents for cotton fabrics. Still other members of the series are poor detergents but have outstanding emulsifying or wetting properties.

The detergency tests to which the specific compounds described in the following examples have been subjected are widely used and well recognized by technologists who have specialized in this field. They consist in washing swatches of standard soiled'fabrics under controlled conditions with a standard solution of the detergent in a Launder-O-Meter instrument, and estimating the degree of soil removal either visually or by means of a photometer. In these tests a minute washing interval and a temperature of 50 C. Were used. The woolen and cotton fabrics were soiled according to the directions given by Crowe in American Dyestuff Reporter 32, page 237 (1943).

The emulsifying powers of these products have been tested by forming emulsions consisting of approximately 100 parts water, 100 parts of medicinal grade white mineral oil, and 0.5 to 5 parts of the surface active agent in question. The emulsions were judged by comparing them, with regard to dispersion and stability, to similar emulsions made with standard emulsifying agents.

In the examples belowa good detergent or good emulsifying agent" will refer to a substance which by the abovetests, show the same order of performance as the commercially successful soaps and synthetic surface active agents Q1 rently used for detergent and emulsifying purposes.

Example I A mixture of 297 g. of the bis-2-hydroxyethylamide of cocoanut fatty acid prepared from Whole distilled cocoanut fatty acids, and 195 g. of N-methylglucamine was heated with agitation at C. to 140 C. At this temperature both substances were liquid and mutually insoluble. After about one hour the two starting materials had reacted sufficiently so that the reaction mass consisted of a single liquid phase. At the end of about two hours the reaction was substantially com lete. The product at room temperature was an amorphous soft solid of pasty consistency readily soluble in water, in lower alcohols and most oxygenated solvents. When tested as above described the product was found to be an excellent detergent for wool and a good detergent for cotton. It was also effective as an emulsifying agent but not outstandingly so.

Example II A mixture of 297 g. of the bis-Z-hydroxyethylamide of cocoanut fatty acid and 181 g. of glucamine was reacted at 130 C. for two hours as described in Example I. The resulting product when tested as above described was found to be a good detergent for W001, particularly in hard water. It was, however, only a fair detergent for cotton. 7

Example III A mixture of 297 g. of the bis-2-hydroxyethylamide of cocoanut fatty acid and 223 g. of N- isopropylglucamine was reacted at 140 C. for 3 hours as described in Example I. The product thus formed was found to be somewhat less readily soluble in water than the corresponding product produced from N-methylglucamine. It was a relatively poor detergent for cotton but an excellent agent for removing large percentages of oil soil from'wool.

Example IV A mixture of 297 g. of the bis-2-hydroxyethylamide of cocoanut fatty acid and 225 g. of N(2- hydroxyethyD-glucamine was. heated at 130-14=0 C. for a period of two hours as described in Example -I. The resulting product was an amor-v phous pasty solid readily soluble in water and a moderately effective detergent for wool and cotton. It was found to be an excellent wetting and foaming agent.

7 Example V Example VI One gram molecular weight of the (2,2'-dihydroxy-t-butyl) amide of cocoanut fatty acid was heated with one gram molecular weight of N- methylglucamine at C. for a period of 4 hours as described in Example I. The resulting product was a soft pasty mass readily soluble in Water- When tested as above described it was Example VII A mixture of 243 g. of highly purified crystalline lauro-(2-hydroxyethyl) amide, and 195 grams of N-methylglucamine was heated to 150 C. for a period of one hour. The resulting product was a. soft translucent wax dispersible in cold water with difficulty but readily soluble in water above 50 C. When tested as above described the product was found to be an excellent detergent for W001 and a good wetting agent in hot solutions. In these respects its behavior was in much contrast to that of lauro-(2-hydroxyethyl) amide itself, which is completely indispersible in water and has no detergent or wetting properties.

Example VIII A mixture of 31.5 g. of highly purified myristobis-(Z-hydroxyethyl) amide, a white crystalline material having a melting point of 49-51" C. and a free fatty acid content of less than 1%, and 19.5 g. of pure N-methylglucamine was heated for 2 hours at 140 C. as described in Example I. The resulting product was completely homogenous in the molten state but a white waxy solid at room temperature. It was readily soluble in Water forming a clear viscous solution of high foaming power. When tested as above described it was found to be an excellent detergent for both wool and cotton, even in water of 400 p. p. m. hardness. Myristobis-(Z-hydroxyethyl) amide, itself is indispersible in cold water and has no detergent power.

Example IX A mixture of 34.3 g. of highly purified palmitobis-(2-hydroxyethyDamide, a white crystalline solid having a melting point of 56-57 C. and a free fatty acid content of 1%, and 19.5 g. of N- methylglucamine was heated to 140 C. for 3 hours. The resulting product was a white wax at room temperature which dissolved readily in hot water. When tested as above described it was found to be an excellent detergent for cotton and a good detergent for W001. This is a marked contrast to the properties of pure palmitobis-(Z-hydroxyethyl) amide which is indispersible in water and has no detergent powers whatsoever.

Now having described by invention what I claim is:

1. The addition product of one molecular equivalent of an amide of a higher fatty acid having the structural formula:

R1 R(IN/ wherein R represents the hydrophobic residue of a carboxylic acid having eight to eighteen carbon atoms, R and R represent radicals selected from the group consisting of hydrogen, unsubstituted alkyl radicals containing l-S carbon atoms, and alkyl radicals containing 1-6 carbon atoms and at least one hydroxyl groups as substituents, at least one hydroxyl group being present in the combination of R and R with at least one molecular equivalent of a glycamine having the structural formula:

wherein R. represents a member selected from the group consisting of hydrogen, an alkyl radical containing 1-6 carbon atoms, and an alkyl radical containing 1-6 carbon atoms and at least one hydroxyl groups, but in no case is said by droxyl group on the alpha carbon; and G represents the radical of a glycitol containing at least 5 carbon atoms, the addition product being formed at a temperature ranging from C. to '150 C.

2. The addition product of one molecular equivalent of an amide of a higher fatty acid having the structural formula:

0 B R- N wherein R represents the hydrophobic residue of a carboxylic acid having eight to eighteen carbon atoms, R and R represent radicals selected from the group consisting of hydrogen, unsubstituted alkyl radicals containing 1-6 carbon atoms, and alkyl radicals containing 1-6 carbon atoms, and at least one hydroxyl groups as substituents, at least one hydroxyl group being present in the combination of R- and R with at least one molecular equivalent of glucamine the addition product being formed at a temperature ranging from 120 C. to C.

3. The addition product of one molecular equivalent of an amide of a higher fatty acid having the structural formula:

wherein R represents the hydrophobic residue of a carboxylic acid having eight to eighteen carbon atoms, R and R represent radicals selected from the group consisting of hydrogen, unsubstituted alkyl radicals containing 1-6 carbon atoms, and alkyl radicals containing 1-6 carbon atoms and at least one hydroxyl groups as substituents, at least one hydroxyl group being present in the combination of R and R with at least one molecular equivalent of N-methylglucamine the addition product being formed at a temperature ranging from 120 C. to 150 C.

4. The addition product of one molecular equivalent of an amide of a higher fatty acid having the structura1 formula:

wherein R represents the hydrophobic residue of a carboxylic acid having eight to thirty carbon atoms, R and R represent radicals selected from the group consisting of hydrogen, unsubstituted alkyl radicals containing 1-6 carbon atoms, and alkyl radicals containing 1-6 carbon atoms and at least one hydroxyl groups as substituents, at least one hydroxyl group being present in the combination of R and R, with at least one molecular equivalent of N-isopropylglucamine, the addition product being formed at a temperature ranging from 120 C. to 150 C.

5. The addition product of one molecular equivalent of an amide of a higher fatty acid having the structural formula:

i RJH/ wherein R represents the hydrophobic residue of a carboxylic acid having eight to eighteen car-- bon atoms, R and R represent radicals selected from the group consisting of hydrogen, unsubstituted alkyl radicals containing 1-6 carbon atoms and at least one hydroxyl groups as substituents, at least one hydroxyl group being present in the combination of R1 .and R with at least one molecular equivalent of N-(2-hydroxyethyDglucamine, the addition products being formed at a temperature ranging from 120 C. to 150 C.

6. The addition product of one molecular equivalent of the bis-Z-hydroxyethylamide of cocoanut fatty acid with at least one molecular equivalent of glucamine.

'7. The addition product of one molecular equivalent of the bis-.2-hydroxyethylamine of cocoanut fatty acid with at least one molecular equivalent of N-methylglucamine.

8. The addition product of one molecular equivalent of the bis-2hydroxyethylamide of cocoanut fatty acid with at least one molecular equivalent of N-isopropylglucamine.

9. The addition product of one molecular equivalent of the bis-2-hydroxyethylamide of cocoanut fatty acid with at least one molecular equivalent of N-(Z-hydroxyethylglucamine).

10. A process for producing new addition products which comprises mixing together one molecular equivalent of an amide of a higher fatty acid having the structural formula:

wherein R represents the hydrophobic residue, of

a carboxylic acid having eight to eighteen car-' bon atoms, R and R represent radicals selected from the group consisting of hydrogen, unsubstituted alkyl radicals containing 1-6 carbon atoms, an alkyl radicals containing 1-6 carbon.

wherein R represents the member selected from the group consisting of hydrogen, an alkyl radical containing 1-6 carbon atoms, and an alkyl radical containing 1-6 carbon atoms and at least one hydroxyl group, but in no case is said hydroxyl group on the alpha carbon; and G represents the radical of a glycitol containing at least 5 carbon atoms andheating the mixture at a temperature ranging from to C. until one of the liquid phases disappears and a 'clear homogeneous product showing a high order of detergency and surface activity is obtained.

ANTHONY M. SCHWARTZ.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,805,355 Bockmuhl et al. May 12, 1931 5 1,985,424 Piggott Dec. 25, 1934 2,089,212 Kritchevsky Aug. 10, 1937 

1. THE ADDITION PRODUCT OF ONE MOLECULAR EQUIVALENT OF AN AMIDE OF A HIGHER FATTY ACID HAVING THE STRUCTURAL FORMULA: 